US9125968B2 - Polymeric/ceramic composite materials for use in medical devices - Google Patents

Polymeric/ceramic composite materials for use in medical devices Download PDF

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US9125968B2
US9125968B2 US11/094,638 US9463805A US9125968B2 US 9125968 B2 US9125968 B2 US 9125968B2 US 9463805 A US9463805 A US 9463805A US 9125968 B2 US9125968 B2 US 9125968B2
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medical balloon
coating
sol
polymer
balloon
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US20060230476A1 (en
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Liliana Atanasoska
Scott Schewe
Robert Warner
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Boston Scientific Scimed Inc
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Boston Scientific Scimed Inc
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Priority to AT06717874T priority patent/ATE509643T1/de
Priority to JP2008504022A priority patent/JP2008534121A/ja
Priority to PCT/US2006/000727 priority patent/WO2006107359A1/fr
Priority to EP20060717874 priority patent/EP1871438B1/fr
Priority to CA 2602451 priority patent/CA2602451A1/fr
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing

Definitions

  • the present invention relates to new and improved materials for the construction of medical devices.
  • balloons mounted on the distal ends of catheters are widely used in medical treatment.
  • a balloon of this type may be used, for example, to widen a vessel into which the catheter is inserted or to force open a blocked vessel.
  • the requirements for the strength and size of the balloon vary widely depending on the balloon's intended use and the vessel size into which the catheter is inserted.
  • balloon angioplasty e.g., percutaneous transluminal coronary angioplasty or “PCTA” in which catheters are inserted over long distances into extremely small vessels and are used to open stenoses of blood vessels by balloon inflation.
  • PCTA percutaneous transluminal coronary angioplasty
  • the medical device community is exploring nanotechnology to enhance medical device performance. For example, in various instances, attempts have been made to incorporate nanoparticles into medical devices through the use of blending and compounding techniques. In some situations, the results have been disappointing, largely due to uneven distribution of the nanoparticles within the material.
  • implantable or insertable medical devices which contain or consist of one or more composite regions. These composite regions, in turn, are formed of a hybrid material that includes a combination of polymer and sol-gel derived ceramic.
  • An advantage of the present invention is that medical devices can be provided with composite regions, which provide for enhanced mechanical characteristics, including enhanced strength, toughness and/or abrasion resistance.
  • FIG. 1 is an external view of a balloon catheter in accordance with the present invention.
  • FIG. 2A is an SEM of an SiO 2 /PEBAX composite film (ca. 30 wt % SiO 2 ).
  • FIG. 2B is an SEM of an SiO 2 /PEBAX composite film (ca. 85 wt % SiO 2 ).
  • the present invention provides implantable or insertable medical devices containing or consisting of one or more composite regions, which contain or consist of a hybrid material that comprises polymer and ceramic.
  • the composite regions may provide, for example, a variety of enhanced mechanical characteristics, including enhanced strength, toughness and abrasion resistance.
  • Medical devices for use in conjunction with the present invention include a wide variety of implantable or insertable medical devices, which are implanted or inserted either for procedural uses or as implants.
  • examples include balloons, catheters (e.g., renal or vascular catheters such as balloon catheters), guide wires, filters (e.g., vena cava filters), stents (including coronary artery stents, peripheral vascular stents such as cerebral stents, urethral stents, ureteral stents, biliary stents, tracheal stents, gastrointestinal stents and esophageal stents), stent grafts, vascular grafts, vascular access ports, embolization devices including cerebral aneurysm filler coils (including Guglilmi detachable coils and metal coils), myocardial plugs, pacemaker leads, left ventricular assist hearts and pumps, total artificial hearts, heart valves, vascular valve
  • the medical devices of the present invention include implantable and insertable medical devices that are used for diagnosis, for systemic treatment, or for the localized treatment of any tissue or organ.
  • Non-limiting examples are tumors; organs including the heart, coronary and peripheral vascular system (referred to overall as “the vasculature”), the urogenital system, including kidneys, bladder, urethra, ureters, prostate, vagina, uterus and ovaries, eyes, lungs, trachea, esophagus, intestines, stomach, brain, liver and pancreas, skeletal muscle, smooth muscle, breast, dermal tissue, cartilage, tooth and bone.
  • treatment refers to the prevention of a disease or condition, the reduction or elimination of symptoms associated with a disease or condition, or the substantial or complete elimination of a disease or condition.
  • Typical subjects also referred to as “patients” are vertebrate subjects, more typically mammalian subjects and even more typically human subjects.
  • the composite regions correspond to entire medical devices. In other embodiments, the composite regions correspond to one or more medical device portions.
  • the composite regions can be in the form of one or more strands which are incorporated into a medical device, in the form of one or more layers formed over all or only a portion of an underlying medical device substrate, and so forth. Layers can be provided over an underlying substrate in a variety of locations, and in a variety of shapes (e.g., in desired patterns), and they can be formed from a variety of composite materials (e.g., different composite compositions may be provided at different locations).
  • Materials for use as underlying medical device substrates include polymeric materials, ceramic materials and metallic materials, as well as other inorganic materials such as carbon- or silicon-based materials.
  • a “layer” of a given material is a region of that material whose thickness is small compared to both its length and width.
  • a layer need not be planar, for example, taking on the contours of an underlying substrate. Layers can be discontinuous (e.g., patterned).
  • FIG. 1 is an exterior view of a balloon catheter 100 .
  • Catheter 100 is shown for the purpose of aiding in the understanding of the present invention and a wide variety of other medical devices, including other catheters, are within the scope of the invention.
  • the catheter 100 shown includes a Luer assembly 110 having a Luer port 114 for liquid introduction and a hub 116 for guide-wire 112 introduction and for manipulation of the catheter 100 .
  • the Luer assembly 110 allows for access to the catheter lumen, such as the injection of inflation fluids or drugs, or the introduction of a guide wire 112 .
  • the balloon catheter 100 illustrated comprises a distal portion 102 that includes a balloon 120 .
  • the distal portion 102 may be of any desired length.
  • the catheter 100 is provided with a composite region in accordance with the invention, which is in the form of a coating 102 c that extends over the entire surface of the distal portion 102 .
  • a therapeutic agent is disposed within or beneath the composite regions, in which cases the composite regions may be referred to as carrier regions or barrier regions.
  • composite carrier region is meant a composite region which further comprises a therapeutic agent and from which the therapeutic agent is released.
  • composite barrier region is meant a composite region which is disposed between a source of therapeutic agent and a site of intended release, and which controls the rate at which therapeutic agent is released.
  • the medical device consists of a composite barrier region that surrounds a source of therapeutic agent.
  • the composite barrier region is disposed over a source of therapeutic agent, which is in turn disposed over all or a portion of a medical device substrate.
  • the composite regions of the present invention are formed of hybrid materials that contain a combination of polymer and ceramic.
  • the composite regions can contain bi-continuous polymeric and ceramic phases, domains of a ceramic phase may be dispersed in a polymer matrix, domains of a polymer phase may be dispersed in domains of a ceramic matrix.
  • the best material properties are obtained when the polymer and ceramic are present in bi-continuous phases, that is, where the ceramic and polymer networks interpenetrate, apparently to the molecular level, so that separate domains are not observed under field emission microscopy or even under transmission electron microscopy.
  • a separate dispersed phase when a separate dispersed phase is present, it desirably will be of nanoscale dimension by which is meant that at least one cross-sectional dimension of the dispersed phase (e.g., the diameter for a spherical or cylindrical phase, the thickness for a ribbon- or plate-shaped phase, etc.) is less than 1 micron (1000 nm), for instance in the range of 0.1 nm to 500 nm, or 1-10 nm. A decrease in such dimensions generally results in an increase in the interfacial area that exists between the polymeric and ceramic phases.
  • multiple polymer and/or ceramic phases may be present.
  • multiple polymer phases may exist where the composite region contains a block copolymer or a blend of different polymers.
  • Polymers for use in the composite regions of the present invention can have a variety of architectures, including cyclic, linear and branched architectures.
  • Branched architectures include star-shaped architectures (e.g., architectures in which three or more chains emanate from a single branch point), comb architectures (e.g., architectures having a main chain and a plurality of side chains) and dendritic architectures (e.g., arborescent and hyperbranched polymers), among others.
  • the polymers for use in the composite regions of the present invention can contain, for example, homopolymer chains, which contain multiple copies of a single constitutional unit, and/or copolymer chains, which contain multiple copies of at least two dissimilar constitutional units, which units may be present in any of a variety of distributions including random, statistical, gradient and periodic (e.g., alternating) distributions.
  • Polymers containing two or more differing homopolymer or copolymer chains are referred to herein as “block copolymers.”
  • Polymers for use in the composite regions of the present invention may be selected, for example, from one or more of the following: polycarboxylic acid polymers and copolymers including polyacrylic acids; acetal polymers and copolymers; acrylate and methacrylate polymers and copolymers (e.g., n-butyl methacrylate); cellulosic polymers and copolymers, including cellulose acetates, cellulose nitrates, cellulose propionates, cellulose acetate butyrates, cellophanes, rayons, rayon triacetates, and cellulose ethers such as carboxymethyl celluloses and hydroxyalkyl celluloses; polyoxymethylene polymers and copolymers; polyimide polymers and copolymers such as polyether block imides and polyether block amides, polyamidimides, polyesterimides, and polyetherimides; polysulfone polymers and copolymers including polyarylsulfones and polyethersulfone
  • polyvinyl ketones such as polyvinylcarbazoles, and polyvinyl esters such as polyvinyl acetates; polybenzimidazoles; ethylene-methacrylic acid copolymers and ethylene-acrylic acid copolymers, where some of the acid groups can be neutralized with either zinc or sodium ions (commonly known as ionomers); polyalkyl oxide polymers and copolymers including polyethylene oxides (PEO); polyesters including polyethylene terephthalates and aliphatic polyesters such as polymers and copolymers of lactide (which includes lactic acid as well as d-, l- and meso lactide), epsilon-caprolactone, glycolide (including glycolic acid), hydroxybutyrate, hydroxyvalerate, para-dioxanone, trimethylene carbonate (and its alkyl derivatives), 1,4-dioxepan-2-one, 1,5-di
  • lactide which includes lactic acid as well
  • Ceramic materials typically are networks of metal or semi-metal oxides or mixed oxide compounds.
  • suitable metals and semi-metals include silicon, zirconium, titanium, aluminum, tin, hafnium, tantalum, molybdenum, tungsten, rhenium and/or iridium oxides, among others.
  • metal/semi-metal atoms designated generally herein as M
  • M-O-M linkages although other interactions are also commonly present including, for example, hydrogen bonding due to the presence of hydroxyl groups such as residual M-OH groups within the ceramic phases.
  • the ceramic employed within the composite regions of the present invention is beneficially formed using sol-gel techniques.
  • the precursor materials used are typically inorganic metallic and semi-metallic salts, metallic and semi-metallic complexes/chelates (e.g., metal acetylacetonate complexes), metallic and semi-metallic hydroxides, or organometallic and organo-semi-metallic compounds (e.g., metal alkoxides and silicon alkoxides and acyloxides). Silicon alkoxides and acyloxides are beneficial due to the variety of formulation options, including co-condensation with related compounds having strong stable C—Si bonds and which can form a strong link between the polymeric and ceramic networks.
  • precursor materials such as those described above are subjected to hydrolysis and condensation (also referred to as polymerization) reactions to form a colloidal suspension, or “sol.”.
  • a colloidal suspension or “sol.”.
  • an alkoxide of choice such as a methoxide, ethoxide, isopropoxide, tert-butoxide, etc.
  • a semi-metal or metal of choice such as silicon, aluminum, zirconium, titanium, tin, hafnium, tantalum, molybdenum, tungsten, rhenium, iridium, etc.
  • a suitable solvent for example, in one or more alcohols.
  • a sol is formed, for example, by adding water or another aqueous solution, such as an acidic or basic aqueous solution (which aqueous solution can further contain organic solvent species such as alcohols), causing hydrolysis and condensation to occur, thereby forming a sol.
  • additional agents can be added, such as agents to control the viscosity and/or surface tension of the sol.
  • the reaction is basically a ceramic network forming process (from G. Kickelbick, “Concepts for the incorporation of inorganic building blocks into organic polymers on a nanoscale” Prog. Polym. Sci., 28 (2003) 83-114, the entire disclosure of which is incorporated herein by reference):
  • R may be a hydrocarbon group, suitably an alkyl group of form 1-20 carbon atoms which optionally may be interrupted with one or more ether oxygen atoms, or an acyl group, for instance formyl, acetyl or benzoyl.
  • n is suitably equal to a valence of M and m is a positive number between 0 and n.
  • the sol may also be a solvent soluble siloxane oligomer composition, for instance prepared by methods described in U.S. Pat. No. 2,490,691, Langwaiter; U.S. Pat. No. 4,950,779, Wengrovius; U.S. Pat. No. 6,140,445, Su et al; and U.S. Pat. No. 6,323,277, Petty et al all expressly incorporated herein by reference in their entirety, or may be obtained by further condensation/hydrolysis reactions of such oligomers.
  • sol enables solid materials to be made in a variety of different forms.
  • thin films can be produced on a substrate by spray coating, coating with an applicator (e.g., by roller or brush), spin-coating, dip-coating, and so forth, of the sol onto the substrate, whereby a “wet gel” is formed.
  • an applicator e.g., by roller or brush
  • spin-coating e.g., by roller or brush
  • dip-coating e.g., by roller or brush
  • the rate of withdrawal from the sol can be varied to influence the properties of the film.
  • Monolithic wet gels can be formed, for example, by placing the sol into or onto a mold or another form (e.g., a sheet) from which the dried gel can be released. The wet gel is then dried.
  • a material commonly called an “aerogel” is obtained. If the gel is dried via freeze drying (lyophilization), the resulting material is commonly referred to as a “cryogel.” Drying at ambient temperature and ambient pressure leads to what is commonly referred to as a “xerogel.” Other drying possibilities are available including elevated temperature drying (e.g., in an oven), vacuum drying (e.g., at ambient or elevated temperatures), and so forth.
  • TEOS tetraethoxysilane
  • TMOS tetramethoxysilane
  • the polymer has substantial non-covalent interactions with the ceramic phase (e.g., due to hydrogen bonding between hydroxyl groups and electronegative atoms within the polymeric and ceramic phases), which prevent macroscopic phase separation.
  • nanoscale phase domains are best achieved by providing covalent interactions between the polymeric and ceramic networks.
  • This result can be achieved via a number of known techniques, including the following: (a) providing species with both polymer and ceramic precursor groups and thereafter conducting polymerization and hydrolysis/condensation simultaneously, (b) providing a ceramic sol with polymer precursor groups (e.g., groups that are capable of participation in a polymerization reaction, such as vinyl groups or cyclic ether groups) and thereafter conducting an organic polymerization step, and/or (c) providing polymers with ceramic precursor groups (e.g., groups that are capable of participation in hydrolysis/condensation, such as metal or semi-metal alkoxide groups), followed by hydrolysis/condensation of the precursor groups.
  • polymer precursor groups e.g., groups that are capable of participation in a polymerization reaction, such as vinyl groups or cyclic ether groups
  • ceramic precursor groups e.g., groups that are capable of participation in hydrolysis/condensation, such as metal or semi
  • an organic/ceramic hybrid composite is prepared by dissolving an organic polymer component in a suitable solvent and adding a ceramic sol precursor.
  • the ratio of the organic polymer component to the ceramic sol precursor may be range from 95/5 to 5/95 on a weight basis, for instance from 80/20 to 20/80.
  • a solution of a strong acid in water is provided to accomplish hydrolysis and condensation of the ceramic sol precursor.
  • the water is provided at a ratio of approximately one mole water per alkoxy equivalent in the ceramic sol source.
  • the mixture may be stirred under reflux to form the sol, for instance for 4-24 hrs, after which it is used to prepare a coating, for instance by casting or coating onto a medical device substrate.
  • the coating is thoroughly dried, optionally with addition of heat and/or vacuum to remove the solvent, and aged for several weeks to allow substantial completion of the ceramic condensation reaction.
  • the organic polymer may be, for instance, a Pebax® block copolymer such as the Pebax® grades 2533, 3533 or 4033, or a mixture thereof.
  • the solvent may be an alcohol solvent such as butanol, propanol, or cyclohexanol or an amide solvent such as dimethylacetamide or a mixture of two or more such solvents.
  • the ceramic sol precursor may be for instance tetraethoxysilane, zirconium isopropoxide, titanium isopropoxide or a mixture thereof.
  • the strong acid may be for instance HCL at 0.05-0.3 moles per liter.
  • the resulting coating has a good combination of toughness, adhesion to the substrate material and abrasion resistance.
  • hybrid species which contain groups that can readily participate in each of these reactions.
  • These hybrid species typically contain organic groups which are capable of participating organic polymerization (typically in conjunction with a comonomer), such as groups containing vinyl (—C ⁇ C), vinylidene (>C ⁇ C), cyclic ether (e.g.,
  • y is 1 to 5
  • isocyanate (—N ⁇ C ⁇ O)
  • amine (—NHR, where R is H or hydrocarbon)
  • carbinol ⁇ C—OH
  • diorganosiloxane groups that can be polymerized to polyorganosiloxanes (for instance dimethylsiloxy, methylphenylsiloxy, diethylsiloxy and like groups).
  • These hybrid species also typically contain additional groups, such as -M(OR) x groups.
  • M is a metal or semi-metal as previously defined
  • x is an integer whose value is at least one less than the valence n of M, typically ranging from 1 to 5 (x may be less than n ⁇ 1 if the same M atom is attached to the hybrid species by more than one bond or is also bonded to one or more monovalent carbon-linked organo groups such as methyl, ethyl, styrylethyl, methacryloxypropyl, glycidoxypropyl, alkylamino, allyl or vinyl), and the various R groups, which may be the same or different, are hydrocarbon or acyl groups, for instance linear, branched or cyclic alkyl groups, aromatic groups or alkyl-aromatic groups of 1 to 10 carbon atoms, and preferably linear or branched alkyl groups having from 1 to 6 carbons, e.g., methyl, ethyl, propyl, isopropyl, and so forth), which are capable of participating in
  • hybrid species may be combined, for example, with (a) one or more optional organic monomers, for instance, vinyl-group-containing monomers (e.g., styrene, among many others), vinylidene-group-containing monomers (e.g., an alkyl(meth)acrylate, an epoxy functional (meth)acrylate, a urethane dimethacrylate and/or a hydroxyalkyl(meth)acrylate), cyclic ether monomers (e.g., vinyl-group-containing monomers (e.g., styrene, among many others), vinylidene-group-containing monomers (e.g., an alkyl(meth)acrylate, an epoxy functional (meth)acrylate, a urethane dimethacrylate and/or a hydroxyalkyl(meth)acrylate), cyclic ether monomers (e.g.,
  • y is 1 to 5, including ethylene oxide, propylene oxide and tetrahydrofuran, and various epoxy functional compounds, especially compounds having two or more epoxy groups per molecule), polyisocyanates, polyamines, polyols and/or diorganosiloxane oligomers (e.g.
  • organometallic or organo-semi-metallic compounds for instance, Si(OR) 4 where R is previously defined (e.g., TEOS or TMOS), (c) water, (d) suitable catalysts, if required, and (e) energy (e.g., heat or photons), if required, at which time organic polymerization and hydrolysis/condensation commences
  • composite materials having polymeric and ceramic phases from a mixture of 3-MPS, methyl methacrylate, TEOS, water, acid, and benzyol peroxide.
  • the hybrid species already has both polymerizable organo and sol-forming -M(OR) x groups on the same molecule, in some cases one or the other of the additional components a) and b) may be avoided, especially if the hybrid species is a functionalized oligomer.
  • Hybrid species can also be used to form composite regions in accordance with routes (b) and (c) described above. For instance, in some cases, such hybrid species are first used to provide a ceramic phase (which contains the organic polymer precursor groups found in the hybrid species) followed by organic polymerization, typically in the presence of one or more comonomers.
  • a hybrid species containing one or more polymerizable organic groups such as a vinyl, vinylidene, cyclic ether or siloxane groups, and one or more inorganic groups, such as -M(OR) x groups (e.g., 3-MPS, SES or 3-GPS, among others) may be combined with a organometallic compound such as a compound of the formula M(OR) n (e.g., TEOS or TMOS) in the presence of water and an acid catalyst such that hydrolysis and condensation take place.
  • a compound of the formula M(OR) n e.g., TEOS or TMOS
  • ceramic phases may be formed which have a range of groups that are capable of participation in polymerization reactions with a range of comonomers, including vinyl-, vinylidene-, cyclic ether- and siloxane-containing monomers, via a range of organic polymerization reactions, including thermal, photochemical, anionic, cationic and radical polymerization methods, such as azobis(isobutyronitrile)- or peroxide-initiated polymerizations and controlled/“living” radical polymerizations, for instance, metal-catalyzed atom transfer radical polymerization (ATRP), stable free-radical polymerization (SFRP), nitroxide-mediated processes (NMP), and degenerative transfer (e.g., reversible addition-fragmentation chain transfer (RAFT)) processes, among others.
  • thermal, photochemical, anionic, cationic and radical polymerization methods such as azobis(isobutyronitrile)- or peroxide-initiated polymerizations and controlled/
  • Step-growth polymerizations such as condensation polymerizations to form polyesters or polyamides, reactions of polyisocyanates and polyols or polyamines to form polyurethane and polyureas, reactions of polyepoxides with polyols, polyamines or polysulfides, and Michael additions of polyamines to compounds having multiple acrylate, maleate, fumerate or nadic groups thereon are further examples of polymerization reactions that may be employed.
  • polymers may be provided with inorganic groups that are capable of participation in hydrolysis/condensation, thereby becoming intimately associated with the ceramic phase.
  • hybrid species such as those discussed above may be employed in organic polymerization reactions via suitable polymerization techniques such as those listed above, typically in the presence of one or more comonomers.
  • the inorganic groups incorporated into the resulting polymer are then available to participate in hydrolysis/condensation, e.g., using techniques such as those discussed above, thereby forming a ceramic phase that is covalently linked to the polymeric phase.
  • preexisting polymers participate in, or provided with inorganic groups that are capable of participating in the hydrolysis/condensation of the ceramic sol.
  • polyol polymers i.e. polymers having 2 or more carbon-linked hydroxyl groups thereon, can be provided with -M(OR) x groups for participation in sol-gel processing.
  • Such polyol polymers include polyether polyols and polyester polyols. Hydroxy groups of a polyol compound may be directly reacted with a compound such as TEOS or tetraethoxytitanate, for instance in the manner of V.
  • hydroxyl groups of a polyol compound such as polymeric polyol can be reacted with a hybrid species to form terminal or pendant groups which are capable of participation in sol/gel hydrolysis/condensation.
  • a polyether of the formula HO R 2 —O r H where R 2 is alkylene (e.g., ethylene, propylene, tetramethylene, etc.) and r is as previously defined, may be reacted with M(OR) n-1 (R—N ⁇ C ⁇ O) to produce (RO) n-1 M-R—NH—CO—O R 2 —O r H or (RO) n-1 M-R—NH—CO—O R 2 —O r O—CO—NH—R-M(OR) n-1 .
  • Epoxy functionalized hydrolyzable silane compounds such as 3-GPS can also be reacted with polyols to give analogous -M(OR) n-1 terminated compounds, for instance -M(OR) n-1 terminated polyethers.
  • the resulting polymer is subjected to an additional polymerization step.
  • a polyether with pendant -M(OR) x groups e.g., a 3-GPS modified polyether having pendant —Si(OEt) 3 groups
  • a polyamide forming monomer e.g., laurolactam
  • additional polyol polymer optionally with additional polyol polymer
  • Polyol polymers are useful components of the compositions employed in the invention because they are amenable to compounding with ceramics, and can form hydrogen bonds with the ceramic network even in cases where they are not covalently linked thereto. This helps prevent macro-domain phase separation of the polymer and ceramic phases. In many cases they are also capable of participating in further polymerization or crosslinking reactions including reaction with polyisocyanates, polyepoxides and the like.
  • polyether-block-polyamides e.g., PEBAX
  • polyesters e.g., polyethylene terephthalate
  • Ether and ester functionalities may also form hydrogen bonds with residual MOH groups in the ceramic phase.
  • A. Lambert III, et al “[Poly(ethylene terephthalate) ionomer]/Silicate Hybrid Materials via Polymer-in Situ Sol-Gel Reactions,” J.
  • ionic bonds in a polymer can also interact with the ceramic network to influence thermal, mechanical, electrical and/or chemical properties of the composite.
  • a component of the sol-gel ceramic may be a catalyst for a concurrent organic polymerization reaction, or a polymer reacting component may catalyze the sol-gel ceramic condensation.
  • organotitanates may catalyze urethane-forming reactions between isocyanates and polyols or an organic amine employed in a reaction with polyisocyanate or polyepoxide may catalyze the alkoxysilane condensation.
  • a particular example of such a system has a 3-GPS derived ceramic network and an amine terminated polyether such as Jeffamine® M600 or M2005 (poly(oxypropylene) diamines), such as described in L.
  • polymer chain segments may be covalently bound to the polymer chains that provide a covalent linkage to a ceramic phase (e.g., in a block copolymer) or another polymer may be provided as a blending component of the composition to modify the physical or chemical properties of the composition.
  • Such polymer chain segments may be selected from the polymers listed above.
  • the additional polymer chain segments may be provided for various reasons. For instance, the polymer chain segments may be introduced (a) to render the composite regions more hydrophilic or hydrophobic, (b) to modulate the release profile of therapeutic agent, if any, (c) to affect the mechanical characteristic of the material, and so forth.
  • Pebax® 4033 pellets are dissolved in 1-butanol/1-propanol (70/30 ratio) at reflux temperature for 4 hours.
  • Casting solutions are dropped into Petri dishes.
  • the solvent is evaporated in an oven at 70° C. Further drying takes place in a vacuum oven at 80° C. for 1 day.
  • microscopy of the resulting films shows elongated separated domains of the inorganic sol-gel derived ceramic component that increased in domain size from the 15/85 TEOS/polymer film, FIG. 2 a , to the 25/75 TEOS/polymer film.
  • the films are useful as tough abrasion resistant coatings for catheters and balloons, for instance catheters and balloons of nylon or Pebax® polymers.
  • the medical devices of the present invention optionally contain one or more therapeutic agents.
  • therapeutic agents “Therapeutic agents,” “drugs,” “pharmaceutically active agents,” “pharmaceutically active materials,” and other related terms may be used interchangeably herein. These terms include genetic therapeutic agents, non-genetic therapeutic agents and cells.
  • therapeutic agents include paclitaxel, sirolimus, everolimus, tacrolimus, Epo D, dexamethasone, estradiol, halofuginone, cilostazole, geldanamycin, ABT-578 (Abbott Laboratories), trapidil, liprostin, Actinomcin D, Resten-NG, Ap-17, abciximab, clopidogrel, Ridogrel, beta-blockers, bARKct inhibitors, phospholamban inhibitors, and Serca 2 gene/protein among others.
  • Numerous additional therapeutic agents useful for the practice of the present invention are also disclosed in U.S. Patent Application 2004/0175406, the entire disclosure of which is incorporated by reference.
  • a wide range of therapeutic agent loadings can be used in connection with the medical devices of the present invention, with the therapeutically effective amount being readily determined by those of ordinary skill in the art and ultimately depending, for example, upon the condition to be treated, the age, sex and condition of the patient, the nature of the therapeutic agent, the nature of the composite region(s), the nature of the medical device, and so forth.
  • various techniques described above involve hydrolysis and condensation, which leads to the formation of a suspension containing a ceramic phase, which is analogous to the “sol” that is formed in sol-gel processing.
  • This suspension also includes a polymer in several techniques. Subsequent removal of water (as well as any other solvent species that may be present), results in the formation of a solid phase, which is analogous to the “gel” in sol-gel processing.
  • such a suspension may be used to directly form a medical device or a medical device component, followed by water/solvent removal.
  • the suspension may be dried and heated to form a melt for further processing.
  • Useful techniques for processing suspensions include pouring, spraying, spray coating, coating with an applicator (e.g., by roller or brush), spin-coating, dip-coating, web coating, techniques involving coating via mechanical suspension including air suspension, ink jet techniques, electrostatic techniques, and combinations of these processes.
  • Useful thermoplastic techniques for processing melts include compression molding, injection molding, blow molding, spinning, vacuum forming and calendaring, as well as extrusion into sheets, fibers, rods, tubes and other cross-sectional profiles of various lengths, and combinations of these processes.
  • the suspension or melt is applied to a substrate to form a composite region.
  • the substrate can correspond, for example, to all or a portion of an implantable or insertable medical device (e.g., a balloon, guide wire or stent, among many others) to which the suspension or melt is applied.
  • the substrate can also correspond, for example, to a template, such as a mold, from which the composite region is removed after solidification.
  • a template such as a mold
  • composite regions for medical devices are formed without the aid of a substrate.
  • therapeutic agents and/or any other optional agents
  • therapeutic and/or other optional agents can be introduced subsequent to the formation of the composite region in some embodiments.
  • the therapeutic agent is dissolved or dispersed within a solvent, and the resulting solution contacted with a previously formed composite region (e.g., using one or more of the application techniques described above, such as dipping, spraying, etc.).
  • composite barrier regions are provided over therapeutic-agent-containing regions in some embodiments of the invention.
  • a composite region can be formed over a therapeutic-agent-containing region, for example, using one of the suspension- or melt-based techniques described above.
  • a previously formed composite region can be adhered over a therapeutic agent containing region.
  • the selection and ratio of the polymer and sol-gel derived ceramic components can be varied to produce a desired release rate of the therapeutic agent. Therefore the in some aspects the invention is particularly directed to an implanted device, especially a stent, graft, valve, vascular access port, embolization device, myocardial plug, pacemaker lead, sutures, orthopedic prostheses, or the like, that is designed for long term residence in the body (for instance 6 months or more).
  • any dependent claim which follows should be taken as alternatively written in a multiple dependent form from all claims which possess all antecedents referenced in such dependent claim, regardless of claim sequence, if such multiple dependent format is an accepted format within the jurisdiction.
  • the following dependent claims should each be also taken as alternatively written in each singly dependent claim format which creates a dependency from an antecedent-possessing claim other than the specific claim listed in such dependent claim.

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US11/094,638 US9125968B2 (en) 2005-03-30 2005-03-30 Polymeric/ceramic composite materials for use in medical devices
EP20060717874 EP1871438B1 (fr) 2005-03-30 2006-01-10 Materiaux composites a base de polymere et de ceramique destines a etre utilises dans des dispositifs medicaux
JP2008504022A JP2008534121A (ja) 2005-03-30 2006-01-10 医療器具に使用するためのポリマー／セラミック複合材料
PCT/US2006/000727 WO2006107359A1 (fr) 2005-03-30 2006-01-10 Materiaux composites a base de polymere et de ceramique destines a etre utilises dans des dispositifs medicaux
AT06717874T ATE509643T1 (de) 2005-03-30 2006-01-10 Polymer/keramik-verbundstoffe zur verwendung in medizinprodukten
CA 2602451 CA2602451A1 (fr) 2005-03-30 2006-01-10 Materiaux composites a base de polymere et de ceramique destines a etre utilises dans des dispositifs medicaux

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Families Citing this family (85)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7713297B2 (en) 1998-04-11 2010-05-11 Boston Scientific Scimed, Inc. Drug-releasing stent with ceramic-containing layer
WO2003002243A2 (fr) 2001-06-27 2003-01-09 Remon Medical Technologies Ltd. Procede et dispositif pour la formation electrochimique d'especes therapeutiques in vivo
CN101090744B (zh) * 2005-01-21 2011-06-15 泰尔茂株式会社 导管及其制造方法
US9125968B2 (en) 2005-03-30 2015-09-08 Boston Scientific Scimed, Inc. Polymeric/ceramic composite materials for use in medical devices
US7914809B2 (en) * 2005-08-26 2011-03-29 Boston Scientific Scimed, Inc. Lubricious composites for medical devices
US8008395B2 (en) * 2005-09-27 2011-08-30 Boston Scientific Scimed, Inc. Organic-inorganic hybrid particle material and polymer compositions containing same
US8840660B2 (en) 2006-01-05 2014-09-23 Boston Scientific Scimed, Inc. Bioerodible endoprostheses and methods of making the same
US8440214B2 (en) 2006-01-31 2013-05-14 Boston Scientific Scimed, Inc. Medical devices for therapeutic agent delivery with polymeric regions that contain copolymers having both soft segments and uniform length hard segments
US8089029B2 (en) 2006-02-01 2012-01-03 Boston Scientific Scimed, Inc. Bioabsorbable metal medical device and method of manufacture
US20070224235A1 (en) 2006-03-24 2007-09-27 Barron Tenney Medical devices having nanoporous coatings for controlled therapeutic agent delivery
US8187620B2 (en) 2006-03-27 2012-05-29 Boston Scientific Scimed, Inc. Medical devices comprising a porous metal oxide or metal material and a polymer coating for delivering therapeutic agents
US8048150B2 (en) 2006-04-12 2011-11-01 Boston Scientific Scimed, Inc. Endoprosthesis having a fiber meshwork disposed thereon
US8815275B2 (en) 2006-06-28 2014-08-26 Boston Scientific Scimed, Inc. Coatings for medical devices comprising a therapeutic agent and a metallic material
US8771343B2 (en) 2006-06-29 2014-07-08 Boston Scientific Scimed, Inc. Medical devices with selective titanium oxide coatings
CA2659761A1 (fr) 2006-08-02 2008-02-07 Boston Scientific Scimed, Inc. Endoprothese avec controle tridimensionnel de desintegration
US20080050415A1 (en) * 2006-08-25 2008-02-28 Boston Scientic Scimed, Inc. Polymeric/ceramic composite materials for use in medical devices
CA2662162A1 (fr) * 2006-08-30 2008-03-06 The University Of British Columbia Revetements composites bioceramiques et procedes de fabrication
US8507639B2 (en) * 2006-09-11 2013-08-13 Boston Scientific Scimed, Inc. Radiopaque amide polymers and medical devices formed thereof
JP2010503469A (ja) 2006-09-14 2010-02-04 ボストン サイエンティフィック リミテッド 薬物溶出性皮膜を有する医療デバイス
CA2663304A1 (fr) 2006-09-15 2008-03-20 Boston Scientific Limited Endoprothese bioerodable a couches inorganiques biostables
JP2010503489A (ja) 2006-09-15 2010-02-04 ボストン サイエンティフィック リミテッド 生体内分解性内部人工器官およびその製造方法
EP2959925B1 (fr) 2006-09-15 2018-08-29 Boston Scientific Limited Dispositifs médicaux et procédés de réalisation desdits dispositifs
ATE517590T1 (de) 2006-09-15 2011-08-15 Boston Scient Ltd Biologisch erodierbare endoprothesen
CA2663762A1 (fr) 2006-09-18 2008-03-27 Boston Scientific Limited Endoprothese
US7981150B2 (en) 2006-11-09 2011-07-19 Boston Scientific Scimed, Inc. Endoprosthesis with coatings
US8425459B2 (en) 2006-11-20 2013-04-23 Lutonix, Inc. Medical device rapid drug releasing coatings comprising a therapeutic agent and a contrast agent
US8998846B2 (en) 2006-11-20 2015-04-07 Lutonix, Inc. Drug releasing coatings for balloon catheters
US8414910B2 (en) 2006-11-20 2013-04-09 Lutonix, Inc. Drug releasing coatings for medical devices
US8414525B2 (en) 2006-11-20 2013-04-09 Lutonix, Inc. Drug releasing coatings for medical devices
US9737640B2 (en) 2006-11-20 2017-08-22 Lutonix, Inc. Drug releasing coatings for medical devices
US8414526B2 (en) 2006-11-20 2013-04-09 Lutonix, Inc. Medical device rapid drug releasing coatings comprising oils, fatty acids, and/or lipids
US9700704B2 (en) 2006-11-20 2017-07-11 Lutonix, Inc. Drug releasing coatings for balloon catheters
US20080175887A1 (en) 2006-11-20 2008-07-24 Lixiao Wang Treatment of Asthma and Chronic Obstructive Pulmonary Disease With Anti-proliferate and Anti-inflammatory Drugs
US20080276935A1 (en) 2006-11-20 2008-11-13 Lixiao Wang Treatment of asthma and chronic obstructive pulmonary disease with anti-proliferate and anti-inflammatory drugs
US8080055B2 (en) 2006-12-28 2011-12-20 Boston Scientific Scimed, Inc. Bioerodible endoprostheses and methods of making the same
US8070797B2 (en) 2007-03-01 2011-12-06 Boston Scientific Scimed, Inc. Medical device with a porous surface for delivery of a therapeutic agent
US8431149B2 (en) 2007-03-01 2013-04-30 Boston Scientific Scimed, Inc. Coated medical devices for abluminal drug delivery
US8343740B2 (en) * 2007-03-29 2013-01-01 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Micro-organ device
US8067054B2 (en) * 2007-04-05 2011-11-29 Boston Scientific Scimed, Inc. Stents with ceramic drug reservoir layer and methods of making and using the same
US20080287984A1 (en) * 2007-05-18 2008-11-20 Jan Weber Medical balloons and methods of making the same
US7976915B2 (en) 2007-05-23 2011-07-12 Boston Scientific Scimed, Inc. Endoprosthesis with select ceramic morphology
US8002823B2 (en) 2007-07-11 2011-08-23 Boston Scientific Scimed, Inc. Endoprosthesis coating
US7942926B2 (en) 2007-07-11 2011-05-17 Boston Scientific Scimed, Inc. Endoprosthesis coating
EP2187988B1 (fr) 2007-07-19 2013-08-21 Boston Scientific Limited Endoprothese pourvue d'une surface anti-encrassement
US8852620B2 (en) * 2007-07-20 2014-10-07 Medtronic Vascular, Inc. Medical devices comprising polymeric drug delivery systems with drug solubility gradients
US20090028785A1 (en) * 2007-07-23 2009-01-29 Boston Scientific Scimed, Inc. Medical devices with coatings for delivery of a therapeutic agent
US8815273B2 (en) 2007-07-27 2014-08-26 Boston Scientific Scimed, Inc. Drug eluting medical devices having porous layers
US7931683B2 (en) 2007-07-27 2011-04-26 Boston Scientific Scimed, Inc. Articles having ceramic coated surfaces
US8221822B2 (en) 2007-07-31 2012-07-17 Boston Scientific Scimed, Inc. Medical device coating by laser cladding
WO2009020520A1 (fr) 2007-08-03 2009-02-12 Boston Scientific Scimed, Inc. Revêtement pour un dispositif médical ayant une aire surfacique accrue
GB0717516D0 (en) * 2007-09-07 2007-10-17 Imp Innovations Ltd Bioactive nanocomposite material
US8052745B2 (en) 2007-09-13 2011-11-08 Boston Scientific Scimed, Inc. Endoprosthesis
US20090104474A1 (en) * 2007-10-17 2009-04-23 Princeton University Functionalized substrates and methods of making same
US8080223B2 (en) * 2007-10-19 2011-12-20 Biointraface, Inc. Method of making a composite from metal oxide and polymer precursors
US8029554B2 (en) 2007-11-02 2011-10-04 Boston Scientific Scimed, Inc. Stent with embedded material
US8216632B2 (en) 2007-11-02 2012-07-10 Boston Scientific Scimed, Inc. Endoprosthesis coating
US7938855B2 (en) 2007-11-02 2011-05-10 Boston Scientific Scimed, Inc. Deformable underlayer for stent
US9114125B2 (en) * 2008-04-11 2015-08-25 Celonova Biosciences, Inc. Drug eluting expandable devices
ES2423504T3 (es) 2008-04-22 2013-09-20 Boston Scientific Scimed, Inc. Dispositivos médicos que tienen un recubrimiento de material inorgánico
US8932346B2 (en) 2008-04-24 2015-01-13 Boston Scientific Scimed, Inc. Medical devices having inorganic particle layers
US7998192B2 (en) 2008-05-09 2011-08-16 Boston Scientific Scimed, Inc. Endoprostheses
US20090306769A1 (en) * 2008-06-06 2009-12-10 Boston Scientific Scimed, Inc. Medical balloon made with hybrid polymer-ceramic material and method of making and using the same
US8236046B2 (en) 2008-06-10 2012-08-07 Boston Scientific Scimed, Inc. Bioerodible endoprosthesis
WO2009155328A2 (fr) 2008-06-18 2009-12-23 Boston Scientific Scimed, Inc. Revêtement d'endoprothèse
US7985252B2 (en) 2008-07-30 2011-07-26 Boston Scientific Scimed, Inc. Bioerodible endoprosthesis
WO2010024898A2 (fr) 2008-08-29 2010-03-04 Lutonix, Inc. Procédés et appareils pour poser un revêtement sur des cathéters à ballonnet
US8226603B2 (en) 2008-09-25 2012-07-24 Abbott Cardiovascular Systems Inc. Expandable member having a covering formed of a fibrous matrix for intraluminal drug delivery
US8049061B2 (en) 2008-09-25 2011-11-01 Abbott Cardiovascular Systems, Inc. Expandable member formed of a fibrous matrix having hydrogel polymer for intraluminal drug delivery
US8076529B2 (en) 2008-09-26 2011-12-13 Abbott Cardiovascular Systems, Inc. Expandable member formed of a fibrous matrix for intraluminal drug delivery
US8382824B2 (en) 2008-10-03 2013-02-26 Boston Scientific Scimed, Inc. Medical implant having NANO-crystal grains with barrier layers of metal nitrides or fluorides
US8389083B2 (en) * 2008-10-17 2013-03-05 Boston Scientific Scimed, Inc. Polymer coatings with catalyst for medical devices
US20100100115A1 (en) * 2008-10-20 2010-04-22 Wilson-Cook Medical Inc. Foam filled intragastric balloon for treating obesity
US8231980B2 (en) 2008-12-03 2012-07-31 Boston Scientific Scimed, Inc. Medical implants including iridium oxide
TWI377226B (en) * 2008-12-31 2012-11-21 Far Eastern New Century Corp Poly (lactic acid) resin composition for preparing transparent and impact-resistant article, article prepared therefrom and preparation process thereof
WO2010101901A2 (fr) 2009-03-02 2010-09-10 Boston Scientific Scimed, Inc. Implants médicaux à tamponnage spontané
US8071156B2 (en) 2009-03-04 2011-12-06 Boston Scientific Scimed, Inc. Endoprostheses
US8287937B2 (en) 2009-04-24 2012-10-16 Boston Scientific Scimed, Inc. Endoprosthese
WO2011119536A1 (fr) 2010-03-22 2011-09-29 Abbott Cardiovascular Systems Inc. Système de pose d'endoprothèse pourvu d'une matrice fibreuse ayant une capacité de rétention améliorée de l'endoprothèse
WO2011119573A1 (fr) 2010-03-23 2011-09-29 Boston Scientific Scimed, Inc. Endoprothèses en métal bioérodable traitées en surface
JP6655785B2 (ja) * 2014-04-17 2020-02-26 パナソニックＩｐマネジメント株式会社 樹脂組成物およびその製造方法並びに半導体装置
JP6442860B2 (ja) * 2014-04-23 2018-12-26 株式会社リコー 前駆体ゾルゲル溶液、電気機械変換素子、液滴吐出ヘッド、及びインクジェット記録装置
US10246594B2 (en) 2016-07-20 2019-04-02 The Boeing Company Corrosion inhibitor-incorporated layered double hydroxide and sol-gel coating compositions and related processes
US10246593B2 (en) 2016-07-20 2019-04-02 The Boeing Company Sol-gel coating compositions including corrosion inhibitor-encapsulated layered double hydroxide and related processes
US10428226B2 (en) 2016-07-20 2019-10-01 The Boeing Company Sol-gel coating compositions and related processes
US10421869B2 (en) 2017-01-09 2019-09-24 The Boeing Company Sol-gel coating compositions including corrosion inhibitor-encapsulated layered metal phosphates and related processes

Citations (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2490691A (en) 1946-10-03 1949-12-06 Du Pont Alkyl polysilicates
US3646155A (en) 1968-12-20 1972-02-29 Midland Silicones Ltd Cross-linking of a polyolefin with a silane
US3950285A (en) 1974-04-04 1976-04-13 Atlantic Richfield Company Preparation of polymeric urethanes from dicarbamates
US4574133A (en) 1984-01-05 1986-03-04 Bp Chemicals Limited Polymer composition
US4753992A (en) 1985-06-06 1988-06-28 Bp Chemicals Limited Polymer composition
US4950779A (en) 1989-12-04 1990-08-21 General Electric Company Nonaqueous method for making silicone oligomers
US5109080A (en) 1989-10-06 1992-04-28 Virginia Tech Intellectual Properties, Inc. High refractive-index ceramic/polymer hybrid material
US5112913A (en) 1984-05-01 1992-05-12 Toray Industries, Inc. Polyester compositions and molded articles therefrom
US5178158A (en) * 1990-10-29 1993-01-12 Boston Scientific Corporation Convertible guidewire-catheter with soft tip
US5210168A (en) 1992-04-02 1993-05-11 Dow Corning Corporation Process for forming siloxane bonds
US5252654A (en) 1991-07-03 1993-10-12 E. I. Du Pont De Nemours And Company Organic-inorganic polymeric composites
US5282998A (en) 1991-06-08 1994-02-01 Huls Aktiengesellschaft Mixtures of linear and cyclic siloxanes or siloxane oligomers and a process for their preparation
US5336731A (en) 1991-10-30 1994-08-09 Quantum Chemical Corporation Fractional melt flow rate polymer powders and process for their preparation
US5354802A (en) 1993-02-11 1994-10-11 Polyplastics Co., Ltd. Resin composition for blow molding and blow molded item made therefrom
WO1994023787A1 (fr) * 1993-04-22 1994-10-27 Rammler David H Catheter a ballon de prelevement
EP0661558A1 (fr) 1993-12-29 1995-07-05 Minnesota Mining And Manufacturing Company Sol gel polymère-céramique
US5556383A (en) 1994-03-02 1996-09-17 Scimed Lifesystems, Inc. Block copolymer elastomer catheter balloons
JPH09165441A (ja) 1995-12-13 1997-06-24 Nishikawa Rubber Co Ltd ポリヒドロキシカルボン酸樹脂の製造方法
US5714257A (en) 1994-11-03 1998-02-03 Kimberly Clark Co Silane modified elastomeric compositions and articles made therefrom
WO1998005269A1 (fr) 1996-08-06 1998-02-12 Purdue Research Foundation Greffe de polymeres hydrophiles biocompatibles sur des surfaces non organiques et metalliques
WO1998046164A1 (fr) 1997-04-11 1998-10-22 Usbiomaterials Corporation Materiau d'implants biodegradables contenant une ceramique bioactive
US5830182A (en) 1994-03-02 1998-11-03 Scimed Life Systems, Inc. Block copolymer elastomer catheter balloons
US5840387A (en) 1995-07-28 1998-11-24 Aegis Biosciences L.L.C. Sulfonated multiblock copolymer and uses therefor
US5849215A (en) 1997-01-08 1998-12-15 The Regents Of The University Of California Highly ordered nanocomposites via a monomer self-assembly in situ condensation approach
US5948314A (en) 1994-10-20 1999-09-07 Hoechst Aktiengesellschaft Composition containing an aerogel, method of producing said composition and the use thereof
US5948946A (en) 1994-01-12 1999-09-07 E. I. Du Pont De Nemours And Company Use of sol-gel derived porous microposite of perfluorinated ion-exchange polymer and metal oxide to isomerize terminal olefins
US5951941A (en) 1994-03-02 1999-09-14 Scimed Life Systems, Inc. Block copolymer elastomer catheter balloons
US5977241A (en) 1997-02-26 1999-11-02 Integument Technologies, Inc. Polymer and inorganic-organic hybrid composites and methods for making same
WO1999064504A1 (fr) 1998-06-05 1999-12-16 Cabot Corporation Reseaux organiques-inorganiques interpenetrants nanoporeux
US6093463A (en) 1997-12-12 2000-07-25 Intella Interventional Systems, Inc. Medical devices made from improved polymer blends
WO2000048552A1 (fr) 1999-02-16 2000-08-24 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Ceramiques organiques
WO2000055213A1 (fr) 1999-03-15 2000-09-21 Multibase S.A. Reticulation de polymeres ou copolymeres de l'acetate de vinyle, elaboration de compositions reticulees dynamiquement et de compositions hybrides organiques-inorganiques conservant un caractere thermoplastique
US6129786A (en) 1997-05-28 2000-10-10 Basf Aktiengesellschaft Composite pigments based on polyalkylenepolyamine-modified nanoparticulate metal oxides and anionic dyes
US6140445A (en) 1998-04-17 2000-10-31 Crompton Corporation Silane functional oligomer
US6146356A (en) 1994-03-02 2000-11-14 Scimed Life Systems, Inc. Block copolymer elastomer catheter balloons
US6232386B1 (en) 1997-02-26 2001-05-15 Integument Technologies, Inc. Polymer composites having an oxyhalo surface and methods for making same
US6271292B1 (en) 1997-02-25 2001-08-07 Bayer Aktiengesellschaft Organic-inorganic hybrid materials
US6395226B1 (en) 1999-04-06 2002-05-28 Medtronic, Inc. Alkoxysilane/alkysilane copolymer coating of medical devices
US6444324B1 (en) 2000-12-01 2002-09-03 Scimed Life Systems, Inc. Lubricated catheter balloon
US6472467B1 (en) 1999-10-21 2002-10-29 Dow Global Technologies Inc. Inorganic/organic compositions
US6476098B1 (en) 1999-05-18 2002-11-05 Orient Chemical Industries, Ltd. Organic-inorganic composite material and process for preparing the same
US6545097B2 (en) 2000-12-12 2003-04-08 Scimed Life Systems, Inc. Drug delivery compositions and medical devices containing block copolymer
US6548590B1 (en) 2000-03-22 2003-04-15 Integument Technologies, Inc. Polymer and inorganic-organic hybrid composites and methods for making and using same
US6569958B1 (en) 2001-10-19 2003-05-27 Dow Corning Corporation Thermoplastic silicone elastomers from compatibilized polyester resins
US6586502B2 (en) 1999-10-21 2003-07-01 Dow Global Technologies Inc. Inorganic/organic compositions
US6599664B2 (en) 1997-08-22 2003-07-29 Yardney Technical Products, Inc. Inorganic gel-polymer electrolyte
US6608129B1 (en) 1997-02-26 2003-08-19 Integument Technologies, Inc. Polymer composites and methods for making and using same
US6629961B1 (en) * 1996-06-26 2003-10-07 Astra Aktiebolag Medical device with hydrophilic coating
WO2004005533A2 (fr) 2002-07-10 2004-01-15 University Of Florida Composite polymere-verre bioactif derive d'un sol-gel
US6686035B2 (en) 1999-02-05 2004-02-03 Waters Investments Limited Porous inorganic/organic hybrid particles for chromatographic separations and process for their preparation
US6737145B1 (en) 1998-10-22 2004-05-18 Ube Nitto Kasei Co., Ltd. Organic-inorganic composite graded material, method for preparation thereof and use thereof
JP2004189917A (ja) 2002-12-12 2004-07-08 Denki Kagaku Kogyo Kk シリカ複合化ラテックス組成物、シリカ複合化ポリクロロプレン系組成物及び製造方法
US20040175406A1 (en) 2003-03-06 2004-09-09 Schwarz Marlene C. Implantable or insertable medical devices containing miscible polymer blends for controlled delivery of a therapeutic agent
US20040181206A1 (en) * 2003-03-12 2004-09-16 Chiu Jessica G. Retrograde pressure regulated infusion
US6794052B2 (en) 1994-10-18 2004-09-21 The Regents Of The University Of California Polymer arrays from the combinatorial synthesis of novel materials
US20050015105A1 (en) 2003-07-18 2005-01-20 Scimed Life Systems, Inc. Protective coatings for medical devices
WO2005082277A1 (fr) * 2004-02-18 2005-09-09 Stanford University Systemes d'administration de medicaments utilisant des films d'oxyde mesoporeux
US6946174B1 (en) 2000-10-12 2005-09-20 Boston Scientific Scimed, Inc. Moisture curable balloon materials
WO2005087284A2 (fr) 2004-03-13 2005-09-22 Dot Gmbh Materiaux composites a base d'acide polysilicique et leur procede de production
US20060020331A1 (en) * 2002-07-12 2006-01-26 Cook Incorporated Coated medical device
US20060199876A1 (en) * 2005-03-04 2006-09-07 The University Of British Columbia Bioceramic composite coatings and process for making same
US20060230476A1 (en) 2005-03-30 2006-10-12 Boston Scientific Scimed, Inc. Polymeric/ceramic composite materials for use in medical devices
US20070048348A1 (en) 2005-08-26 2007-03-01 Liliana Atanasoska Lubricious composites for medical devices
US20070072978A1 (en) 2005-09-27 2007-03-29 Boston Scientific Scimed, Inc. Organic-inorganic hybrid particle material and polymer compositions containing same
US7365126B2 (en) 2005-09-16 2008-04-29 Boston Scientific Scimed, Inc. Medical device articles formed from polymer-inorganic hybrids prepared by ester-alkoxy transesterification reaction during melt processing
US20090306769A1 (en) 2008-06-06 2009-12-10 Boston Scientific Scimed, Inc. Medical balloon made with hybrid polymer-ceramic material and method of making and using the same

Patent Citations (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2490691A (en) 1946-10-03 1949-12-06 Du Pont Alkyl polysilicates
US3646155A (en) 1968-12-20 1972-02-29 Midland Silicones Ltd Cross-linking of a polyolefin with a silane
US3950285A (en) 1974-04-04 1976-04-13 Atlantic Richfield Company Preparation of polymeric urethanes from dicarbamates
US4574133A (en) 1984-01-05 1986-03-04 Bp Chemicals Limited Polymer composition
US5112913A (en) 1984-05-01 1992-05-12 Toray Industries, Inc. Polyester compositions and molded articles therefrom
US4753992A (en) 1985-06-06 1988-06-28 Bp Chemicals Limited Polymer composition
US5109080A (en) 1989-10-06 1992-04-28 Virginia Tech Intellectual Properties, Inc. High refractive-index ceramic/polymer hybrid material
US4950779A (en) 1989-12-04 1990-08-21 General Electric Company Nonaqueous method for making silicone oligomers
US5178158A (en) * 1990-10-29 1993-01-12 Boston Scientific Corporation Convertible guidewire-catheter with soft tip
US5282998A (en) 1991-06-08 1994-02-01 Huls Aktiengesellschaft Mixtures of linear and cyclic siloxanes or siloxane oligomers and a process for their preparation
US5252654A (en) 1991-07-03 1993-10-12 E. I. Du Pont De Nemours And Company Organic-inorganic polymeric composites
US5336731A (en) 1991-10-30 1994-08-09 Quantum Chemical Corporation Fractional melt flow rate polymer powders and process for their preparation
US5210168A (en) 1992-04-02 1993-05-11 Dow Corning Corporation Process for forming siloxane bonds
US5354802A (en) 1993-02-11 1994-10-11 Polyplastics Co., Ltd. Resin composition for blow molding and blow molded item made therefrom
WO1994023787A1 (fr) * 1993-04-22 1994-10-27 Rammler David H Catheter a ballon de prelevement
EP0661558A1 (fr) 1993-12-29 1995-07-05 Minnesota Mining And Manufacturing Company Sol gel polymère-céramique
US6160190A (en) 1994-01-12 2000-12-12 E. I. Du Pont De Nemours And Company Alkylation of aromatic compounds using a sol-gel derived porous microcomposite of perfluorinated ion-exchange polymer and metal oxide
US5948946A (en) 1994-01-12 1999-09-07 E. I. Du Pont De Nemours And Company Use of sol-gel derived porous microposite of perfluorinated ion-exchange polymer and metal oxide to isomerize terminal olefins
US5830182A (en) 1994-03-02 1998-11-03 Scimed Life Systems, Inc. Block copolymer elastomer catheter balloons
US5951941A (en) 1994-03-02 1999-09-14 Scimed Life Systems, Inc. Block copolymer elastomer catheter balloons
US6146356A (en) 1994-03-02 2000-11-14 Scimed Life Systems, Inc. Block copolymer elastomer catheter balloons
US5556383A (en) 1994-03-02 1996-09-17 Scimed Lifesystems, Inc. Block copolymer elastomer catheter balloons
US6794052B2 (en) 1994-10-18 2004-09-21 The Regents Of The University Of California Polymer arrays from the combinatorial synthesis of novel materials
US5948314A (en) 1994-10-20 1999-09-07 Hoechst Aktiengesellschaft Composition containing an aerogel, method of producing said composition and the use thereof
US5714257A (en) 1994-11-03 1998-02-03 Kimberly Clark Co Silane modified elastomeric compositions and articles made therefrom
US5840387A (en) 1995-07-28 1998-11-24 Aegis Biosciences L.L.C. Sulfonated multiblock copolymer and uses therefor
JPH09165441A (ja) 1995-12-13 1997-06-24 Nishikawa Rubber Co Ltd ポリヒドロキシカルボン酸樹脂の製造方法
US6629961B1 (en) * 1996-06-26 2003-10-07 Astra Aktiebolag Medical device with hydrophilic coating
WO1998005269A1 (fr) 1996-08-06 1998-02-12 Purdue Research Foundation Greffe de polymeres hydrophiles biocompatibles sur des surfaces non organiques et metalliques
US5849215A (en) 1997-01-08 1998-12-15 The Regents Of The University Of California Highly ordered nanocomposites via a monomer self-assembly in situ condensation approach
US6271292B1 (en) 1997-02-25 2001-08-07 Bayer Aktiengesellschaft Organic-inorganic hybrid materials
US6608129B1 (en) 1997-02-26 2003-08-19 Integument Technologies, Inc. Polymer composites and methods for making and using same
US6232386B1 (en) 1997-02-26 2001-05-15 Integument Technologies, Inc. Polymer composites having an oxyhalo surface and methods for making same
US5977241A (en) 1997-02-26 1999-11-02 Integument Technologies, Inc. Polymer and inorganic-organic hybrid composites and methods for making same
WO1998046164A1 (fr) 1997-04-11 1998-10-22 Usbiomaterials Corporation Materiau d'implants biodegradables contenant une ceramique bioactive
US5977204A (en) 1997-04-11 1999-11-02 Osteobiologics, Inc. Biodegradable implant material comprising bioactive ceramic
US6129786A (en) 1997-05-28 2000-10-10 Basf Aktiengesellschaft Composite pigments based on polyalkylenepolyamine-modified nanoparticulate metal oxides and anionic dyes
US6599664B2 (en) 1997-08-22 2003-07-29 Yardney Technical Products, Inc. Inorganic gel-polymer electrolyte
US6093463A (en) 1997-12-12 2000-07-25 Intella Interventional Systems, Inc. Medical devices made from improved polymer blends
US6323277B1 (en) 1998-04-17 2001-11-27 Witco Corporation Bridged silicone oligomers and curable compositions containing same
US6140445A (en) 1998-04-17 2000-10-31 Crompton Corporation Silane functional oligomer
US6825260B2 (en) 1998-06-05 2004-11-30 Cabot Corporation Nanoporous interpenetrating organic-inorganic networks
WO1999064504A1 (fr) 1998-06-05 1999-12-16 Cabot Corporation Reseaux organiques-inorganiques interpenetrants nanoporeux
US6737145B1 (en) 1998-10-22 2004-05-18 Ube Nitto Kasei Co., Ltd. Organic-inorganic composite graded material, method for preparation thereof and use thereof
US6686035B2 (en) 1999-02-05 2004-02-03 Waters Investments Limited Porous inorganic/organic hybrid particles for chromatographic separations and process for their preparation
WO2000048552A1 (fr) 1999-02-16 2000-08-24 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Ceramiques organiques
WO2000055213A1 (fr) 1999-03-15 2000-09-21 Multibase S.A. Reticulation de polymeres ou copolymeres de l'acetate de vinyle, elaboration de compositions reticulees dynamiquement et de compositions hybrides organiques-inorganiques conservant un caractere thermoplastique
US6395226B1 (en) 1999-04-06 2002-05-28 Medtronic, Inc. Alkoxysilane/alkysilane copolymer coating of medical devices
US6476098B1 (en) 1999-05-18 2002-11-05 Orient Chemical Industries, Ltd. Organic-inorganic composite material and process for preparing the same
US6472467B1 (en) 1999-10-21 2002-10-29 Dow Global Technologies Inc. Inorganic/organic compositions
US6586502B2 (en) 1999-10-21 2003-07-01 Dow Global Technologies Inc. Inorganic/organic compositions
US6548590B1 (en) 2000-03-22 2003-04-15 Integument Technologies, Inc. Polymer and inorganic-organic hybrid composites and methods for making and using same
US6946174B1 (en) 2000-10-12 2005-09-20 Boston Scientific Scimed, Inc. Moisture curable balloon materials
US6444324B1 (en) 2000-12-01 2002-09-03 Scimed Life Systems, Inc. Lubricated catheter balloon
US6545097B2 (en) 2000-12-12 2003-04-08 Scimed Life Systems, Inc. Drug delivery compositions and medical devices containing block copolymer
US6569958B1 (en) 2001-10-19 2003-05-27 Dow Corning Corporation Thermoplastic silicone elastomers from compatibilized polyester resins
WO2004005533A2 (fr) 2002-07-10 2004-01-15 University Of Florida Composite polymere-verre bioactif derive d'un sol-gel
US20060020331A1 (en) * 2002-07-12 2006-01-26 Cook Incorporated Coated medical device
JP2004189917A (ja) 2002-12-12 2004-07-08 Denki Kagaku Kogyo Kk シリカ複合化ラテックス組成物、シリカ複合化ポリクロロプレン系組成物及び製造方法
US20040175406A1 (en) 2003-03-06 2004-09-09 Schwarz Marlene C. Implantable or insertable medical devices containing miscible polymer blends for controlled delivery of a therapeutic agent
US20040181206A1 (en) * 2003-03-12 2004-09-16 Chiu Jessica G. Retrograde pressure regulated infusion
WO2005014075A1 (fr) 2003-07-18 2005-02-17 Boston Scientific Limited Revetements de protection pour dispositifs medicaux
US20050015105A1 (en) 2003-07-18 2005-01-20 Scimed Life Systems, Inc. Protective coatings for medical devices
WO2005082277A1 (fr) * 2004-02-18 2005-09-09 Stanford University Systemes d'administration de medicaments utilisant des films d'oxyde mesoporeux
WO2005087284A2 (fr) 2004-03-13 2005-09-22 Dot Gmbh Materiaux composites a base d'acide polysilicique et leur procede de production
US20060199876A1 (en) * 2005-03-04 2006-09-07 The University Of British Columbia Bioceramic composite coatings and process for making same
US20060230476A1 (en) 2005-03-30 2006-10-12 Boston Scientific Scimed, Inc. Polymeric/ceramic composite materials for use in medical devices
WO2006107359A1 (fr) 2005-03-30 2006-10-12 Boston Scientific Limited Materiaux composites a base de polymere et de ceramique destines a etre utilises dans des dispositifs medicaux
US20070048348A1 (en) 2005-08-26 2007-03-01 Liliana Atanasoska Lubricious composites for medical devices
US7365126B2 (en) 2005-09-16 2008-04-29 Boston Scientific Scimed, Inc. Medical device articles formed from polymer-inorganic hybrids prepared by ester-alkoxy transesterification reaction during melt processing
US20070072978A1 (en) 2005-09-27 2007-03-29 Boston Scientific Scimed, Inc. Organic-inorganic hybrid particle material and polymer compositions containing same
US20090306769A1 (en) 2008-06-06 2009-12-10 Boston Scientific Scimed, Inc. Medical balloon made with hybrid polymer-ceramic material and method of making and using the same

Non-Patent Citations (30)

* Cited by examiner, † Cited by third party
Title
A. Lambert III, et al, "[Poly(ethylene terephthalate) ionomer]/Silicate Hybrid Materials via Polymer-in Situ Sol-Gel Reactions," J. Applied Polymer Science, 84, 1749-1761 (2002).
C. Lacroix et al., "Properties of PETG/EVA blends: 2. Study of reactive compatibilization by n.m.r. spectroscopy and linear viscoelastice properties," Polymer vol. 37 No. 14, (1996) 2949-2956.
Correia et al., "Sol-gel-derived POE/siliceous hybrids doped with Na+ ions: morphology and ionic conductivity," Solid State Ionics, vol. 156, pp. 85-93, (2003).
G. Kickelbick, "Concepts for the incorporation of inorganic building blocks into organic polymers on a nanoscale" Prog. Polym. Sci., 28 (2003) 83-114.
H. Huang et al, "Structure-property behavior of hybrid materials incorporating tetraethoxysilane with multifunctional poly(tetramethylene oxide)" Polymer, 30, 2001-2012 (1989).
Honma et al., "Protonic conducting organic/inorganic nanocomposites for polymer electrolyte membrane," Journal of Membrane Science, vol. 185, pp. 83-94, (2001).
Honma et al., "Protonic conducting properties of sol-gel derived organic/inorganic nanocomposite membranes doped with acidic functional molecules," Solid State Ionics, vol. 120, pp. 225-264, (1999).
Honma et al., "Synthesis of organic/inorganic protonic conducting membrane through sol-gel processes," Solid State Ionics, vol. 118, pp. 29-36, (1999).
J. Pyun et al, "Synthesis of Nanocomposite Organic/Inorganic Hybrid Materials Using Controlled/ 'Living' Radical Polymerization," Chem. Mater., 13:3436-3448 (2001).
K. Haas et al, "Hybrid Inorganic/Organic Polymers with Nanoscale Building Blocks; Precursors, Processing, Properties and Applications," Rev. Adv. Mater. Sci., 5 (2003) 47-52.
L. Mat{hacek over (e)}jka, et al, "Block-copolymer organic-inorganic networks. Structure, morphology and thermomechanical properties," Polymer, 45 (2004) 3267-3276.
L. Shen et al, "In situ polymerization and characterization of polyamide-6/silica nanocomposite derived from water glass," Polymer International, 53, 1153-1160 (2004).
Masuru Okabe et al., Phenomenological Study on Sol-Gel Transition of Linear Low Density Polyethylene in Organic Solvents, 1985, Journal of Applied Polymer Science, vol. 30, pp. 4735-4743. *
P. Xu, "Polymer-Ceramic Nanocomposites," Encyclopedia of Materials: Science and Technology, Elsevier Science Ltd. (2000).
Park et al., A Paclitaxel-eluting Stent for the prevention of Cornonary Restenosis, ACC Current Journal Review, 2003, p. 65. *
PCT Written Opinion for PCT/US2006/000727, which claims priority to U.S. Appl. No. 11/094,638, filed Sep. 30, 2007.
Pyun and Matyjaszewski, "Synthesis of Nanocomposite Organic/Inorganic Hybrid Materials Using Controlled/ "Living" Radical Polymerization," Chem. Mater., 13:3436-3448 (2001).
R. Zoppi et al, "Hybrids of Poly(ethylene oxide-b-amide-6) and ZrO2 Sol-gel: Preparation, Characterization, and Application in Processes of Membranes Separation," Advances in Polymer Technology, vol. 21, No. 1, 2-16 (2002).
S.K. Young et al, "Covalent and non-covalently coupled polyester-inorganic composite materials," Polymer 43, (2002) 6101-6114.
Sang-Hoon Rhee, "Bone-like apatite-forming ability and mechanical properties of poly(epsilon-caprolactone)/silica hybrid as a function of poly(epsilon-caprolactone) content," Biomaterials 25 (2004) 1167-1175.
Sang-Hoon Rhee, "Bone-like apatite-forming ability and mechanical properties of poly(ε-caprolactone)/silica hybrid as a function of poly(ε-caprolactone) content," Biomaterials 25 (2004) 1167-1175.
Sforça, M. L., et al., "Hybrid membranes based on SiO2/polyether-b-polyamide: morphology and applications," Journal of Applied Polymer Science, vol. 82, pp. 178-185, 2001.
Tecoflex "Next-Bio Basics" pp. 1-2, Mar. 12, 2010.
V. Bounor-Legare et al., "A new route for organic-inorganic hybrid material syntheses through reactive processing without solvent," Polymer 45 (2004) 1485-1493.
V. Bounor-Legare et al., "Ethylene-co-vinyl acetate copolymer crosslinking through ester-alkoxysilane exchange reaction catalyzed by dibutyltin oxide: mechanistic aspects investigated through model compounds by multinuclear NMR spectroscopy," Polym. Int. 53: 484-494 (2004).
V. Bounor-Legare et al., "New transecterification between ester and alkoxysilane groups: application to ethylene-co-vinyl acetate copolymer crosslinking," Polymer 43 (2002) 6085-6092.
V. de Zea Bermudez et al., "Sol-Gel Derived Urea Cross-Linked Organically Modified Silicates. 1. Room Temperature Mid-Infrared Spectra," Chem. Mater., vol. 11, pp. 569-580, (1999).
V. Munchow, et al, "Poly[(oligoethylene glycol) dihydroxytitanate] as organic-inorganic polymer-electrollytes," Electrochimica Acta, 45 (2000) 1211-1221.
Y. Goutille et al., "Crosslinking in the melt of EVA using tetrafunctional silane: gel time from capillary rheometry," Polymer 44 (2003) 3165-3171.
Yano, S. et al., "Physical properties and structure of organic-inorganic hybrid materials produced by sol-gel process," Materials Science and Engineering, vol. C6, pp. 75-90, (1998).

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